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Fine Tuning and Specific Binding Sites with a Porous HydrogenBonded Metal-Complex Framework for Gas Selective Separations Zongbi Bao, Danyan Xie, Ganggang Chang, Hui Wu, Liangying Li, Wei Zhou, Hailong Wang, Zhiguo Zhang, Huabin Xing, Qiwei Yang, Michael J. Zaworotko, Qilong Ren, and Banglin Chen J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b13706 • Publication Date (Web): 14 Mar 2018 Downloaded from http://pubs.acs.org on March 14, 2018
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Fine Tuning and Specific Binding Sites with a Porous HydrogenBonded Metal-Complex Framework for Gas Selective Separations Zongbi Bao,† Danyan Xie,† Ganggang Chang,†,Ⅱ Hui Wu,§ Liangying Li,† Wei Zhou,*,§ Hailong Wang,‡ Zhiguo Zhang,† Huabin Xing,† Qiwei Yang,† Michael J. Zaworotko,⊥ Qilong Ren*,† and Banglin Chen *,‡ †Key
Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. China ‡Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA §NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102, USA ⅡSchool ⊥
of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, P. R. China Department of Chemical and Environmental Sciences, University of Limerick, Limerick, Republic of Ireland
ABSTRACT: Research on HOFs has been developed for quite a long time; however, those with both established permanent porosities and functional properties are extremely rare due to weak hydrogen-bonding interactions among molecular organic linkers which are much more fragile and difficult to stabilize. Herein, through judiciously combining the superiority of both the moderately stable coordination bonds in MOFs and hydrogen bonds, we have realized a microporous hydrogenbonded metal-complex or metallotecton framework HOF-21, which not only shows permanent porosity but also exhibits highly selective separation performance of C2H2/C2H4 at room temperature. The outstanding separation performance can be ascribed to sieving effect confined by the fine-tuning pores and the superimposed hydrogen-bonding interaction between C2H2 and SiF62- on both ends as validated by both modeling and neutron powder diffraction experiments. More importantly, the collapsed HOF-21 can be restored by simply immersing it into water or salt solution. To the best of our knowledge, such extraordinary water stability and restorability of HOF-21 was observed for the first time in HOFs, underlying the bright perspective of such new HOF materials for their industrial usage.
INTRODUCTION
Novel porous materials have the promise to gradually weed out the traditional costly and energy-intensive technologies such as amine scrubbing and cryogenic distillation, through the adsorption-based gas separations.1 Over the past two decades, extensive research endeavors on porous materials have eventually led to the emergence of porous metal-organic frameworks (MOFs)2 and covalentorganic frameworks (COFs),3 whose separation selectivities and capacities have surpassed those traditional zeolite materials for some important gas separations. Compared with MOFs and COFs, which are self-assembled through coordination and covalent bonding of their corresponding building units; hydrogen-bonded organic frameworks (HOFs), self-assembled frameworks by utilizing intermolecular hydrogen-bonding interactions, have recently been realized as potential porous materials as well. Although their porosities might be not as high as MOFs and COFs, HOFs are superior to MOFs and COFs because of their facile synthesis and characterization, as well as easy purification and regeneration by simple soaking.4 Furthermore, high porosities of porous materials are not the pre-requisites for their gas separation applications. In fact, most porous materials exhibiting excellent performance for gas separations are those of moderate porosities with Brunauer–Emmett–Teller (BET) surface areas less than 1000 m2/g, which means that HOFs are very promising
candidates for gas separations. Indeed, a few HOFs have been established for their gas separations. Because hydrogen bonding interactions are much weaker than coordination and covalent bonds, it is still very challenging to stabilize the HOFs in which most frameworks collapsed during the framework activations. Current research on HOFs has been mainly focused on the usage of pure organic linkers and/or building blocks. As demonstrated in the development of mixed metalorganic frameworks (M’MOFs),5 incorporation of metalcomplexes and/or metallotectons into the porous materials can readily generate unique pore structures, topologies and functionalities; however, HOFs with metal-complexes as the building units have been rarely explored.6 The usage of [Cu2(ade)4] (ade= adenine) to construct porous HOFs by Zaworotko group,6b as exemplified by [Cu2(ade)4]·2TiF6 (MPM-1-TIFSIX), has attracted our great interests. Such a simple metal-complex strategy has not only opened a new methodology to construct porous HOFs in which some unconventional organic linkers can be readily assembled into the porous materials, but also provided diverse ways to tune and functionalize the pores through the deliberate choices of metal clusters and the accessible sites on the metal centers. Herein we report a novel HOF assembled from [Cu2(ade)4] with the co-supporting SiF62- anions. To our great surprise, the resulting HOF [Cu2(ade)4(H2O)2]·2SiF6 (termed HOF-21) has a significant-
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ly different structure from MPM-1-TIFSIX because of the occupancy of water molecules on the copper sites in HOF21. Accordingly, the HOF-21 has a smaller pore sizes of 3.6 Å than MPM-1-TIFSIX of 7.1 Å Furthermore, the specific binding sites of SiF62- on the pore surfaces further induce their preferential recognition of C2H2 molecules. Thus, HOF-21 exhibits much higher and efficient C2H2/C2H4 separation properties than MPM-1-TIFSIX, as clearly demonstrated by breakthrough experiments. Neutron diffraction studies and density-functional theory (DFT) calculations further confirm the recognition mechanisms. HOF-21 shows exceptionally high stability, and can be easily regenerated through simple soaking in the water.
EXPERIMENTAL SECTION
All Reagents and solvents were used as received without any purification. Powder X-ray diffraction (PXRD) patterns of the samples were recorded with aXPert diffractometer (Panalytical Corp., Netherlands) using Cu Ka (λ=0.1543 nm) radiation at 40 kV from 5o to 40o (2θ angle range) with a scanning step size of 0.02o. Thermogravimetric analysis (TGA) of HOF-21 was performed at a heating rate of 10 °C/min under a nitrogen flow on a thermogravimetric analyzer Pyris-1 TGA (PerkinElmer, USA). Infrared spectra were obtained using a Fourier transform infrared spectroscopy Nicolet iS10 (Thermo Fisher Scientific Inc., USA). Elemental analysis (EA) was carried out on Vario MICRO Elemental Analyzer (Elementar Company, Germany). Preparation of [Cu2(ade)4(H2O)2](SiF6)2 (HOF-21): At room temperature, 0.152 mmol (20.5 mg) of adenine dissolved in 3 mL of 1:1 acetonitrile/H2O was layered above 3 mL of an aqueous solution containing 0.076 mmol (17.75 mg) of Cu(NO3)2·3H2O and 0.076 mmol (13.53 mg) of (NH4)2SiF6. 1 mL of 1:1 acetonitrile/H2O was layered between the top and bottom solutions to slow the rate of reaction. Dark blue, rectangular prismatic crystals formed in 30% yield (based on the weight of HOF-21a) after 4 days. These crystals were suitable for structure resolution by single-crystal X-ray crystallography. Unless indicated otherwise, this synthetic methodology was used to prepare sample for gas sorption measurements and breakthrough experiments. IR (KBr pellet): 3131 (m), 1658 (s), 1625 (m), 1605 (m), 1589 (w), 1459 (s), 1411 (s), 1351 (w), 1316 (s), 1236 (s), 1179 (w), 1029 (m), 970 (w), 936 (w), 788 cm-1 (m); elemental analysis calcd (%) for [Cu2(ade)4(H2O)2](SiF6)2: C 24.30, H 2.43, N 28.34; found 24.21, H 2.56, N 28.27. Activation of HOF-21 (denoted as HOF-21a): The assynthesized HOF-21 was exchanged with fresh methanol several times to displace water molecules and then evacuated under dynamic vacuum at 298 K for 24 h to obtain activated HOF-21 before confirming the porosity. Restoration of framework-collapsed HOF-21a: The pore structure of HOF-21a collapsed when it was evacuated under dynamic vacuum at temperature of 423 K. The collapsed frameworks (~100 mg) were soaked into pure water (20 mL) or an aqueous solution (20 mL) containing (NH4)2SiF6 (0.50 mmol, 89.0 mg) for 48 h. The regenerated frameworks were collected by centrifugation, and then
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activated under a high vacuum at room temperature for 24 h prior to porosity measurements. Single Crystal X-ray Diffraction of HOF-21. Single crystal X-ray diffraction data of as-synthesized HOF-21 were collected at 293 K on a Gemini A Ultra diffractometer graphite-monochromatic enhanced Mo radiation ( λ = 0.71073). The structure was solved by direct methods and refined by full-matrix least-squares methods with the SHELXTL program package. The solvent molecules in assynthesized HOF-21 crystal are highly disordered. The SQUEEZE subroutine of the PLATON software suite was used to remove the scattering from the highly disordered guest molecules. Single crystal X-ray diffraction reveals that HOF-21 crystallizes in the orthorhombic space group Cmcm (see Table 1). Table 1. Crystal data and structure refinement for assynthesized HOF-21 Identification code
HOF-21
Empirical formula
C20H24Cu2F12N20O2Si2
Formula weight
987.85
Temperature (K)
293 K
Crystal system
Orthorhombic
Space group
Cmcm a=16.9982 Å(8), b=11.0287 Å (5),
Cell
c=21.3180 Å (11)
α=90o, β=91.676o, γ=90o Volume (Å3) Mu
(mm-1)
3996.4(3) 1.231
ρ (g·cm-3)
1.642
Z
4
F000
1976.0
F000’
1980.24
h, k, lmax
20, 13, 25
Nref
1953
Tmin, Tmax
0.633, 0.753
Tmin’
0.620
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(a)
(c)
(b)
(d)
Figure 1. X-ray crystal structure of HOF-21. (a) The building block of MPM-1-TIFSIX, discrete dinuclear paddle-wheel ionic complex features four adenine ligands in equatorial positions and TiF2- in axial positions, and 3D framework packing along the c axis showing the 1D channels of about 7.1 Å in diameter. (b) The building block of HOF-21, discrete dinuclear paddle-wheel ionic complex features four adenine ligands in equatorial positions and two water molecules in axial positions, and 3D framework packing along the c axis showing the 1D channels of about 3.6 Å in diameter. (c) Hydrogen-bonding interaction networks between the SiF62and the building blocks viewing along the b axis. (d) Hydrogen-bonding interactions among building blocks viewing along c axis in HOF-21. Cu, green; Si, orange; Ti, yellow; F, light green; N, blue; O, red; C, gray; H, white.
Neutron diffraction experiment. Neutron powder diffraction data were collected using the BT-1 neutron powder diffractometer at the NIST Center for Neutron Research. A Ge(311) monochromator with a 75° take-off angle, lambda = 2.0787(2) Å, and in-pile collimation of 60 minutes of arc were used. Data were collected over the range of 1.3-166.3° 2-Theta with a step size of 0.05°. Fully activated HOF-21a sample was loaded in a vanadium can equipped with a capillary gas line and a packless valve. A closed-cycle He refrigerator was used for sample temperature control. The bare HOF-21a sample was measured first at temperatures of 200 K. To probe the gas adsorption locations, a pre-determined amount of C2D2 was loaded into the sample at room temperature. (Note: deuterated gas C2D2 was used to avoid the large incoherent neutron scattering background that would be produced by the hydrogen in C2H2) The sample was then slowly cooled to 200 K
before diffraction data were collected. Rietveld structural refinements were performed on the diffraction data using the GSAS package.7 Due to the large number of atoms in the crystal unit cell, the adenine ligand molecule and the gas molecule were both treated as rigid bodies in the Rietveld refinement (to limit the number of variables), with the molecule orientation and center of mass freely refined. Final refinement on the positions/orientations of the rigid bodies, thermal factors, occupancies, lattice parameters, background, and profiles converges with satisfactory Rfactors.
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Density-functional theory calculations. Our Firstprinciples density-functional theory (DFT) calculations were performed using the Quantum-Espresso package.8 A semi-empirical addition of dispersive forces to conventional DFT9 was included in the calculation to account for van der Waals interactions. We used Vanderbilt-type ultrasoft pseudopotentials and the generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerof (PBE) exchange correlation. A cutoff energy of 544 eV and a 2×4×2 k-point mesh (generated using the Monkhosrt Pack scheme) were found to be enough for total energy to converge within 0.01 meV/atom. We first optimized the HOF-21a structures. C2H2 gas molecule was then introduced to the optimized HOF structure at the experimentally identified adsorption site, followed by a full structural relaxation. To obtain the gas binding energy, a gas molecule placed in a supercell with the same cell dimensions was also relaxed as a reference. The static binding energy (at T = 0 K) was then calculated using: EB = E(HOF-21a) + E(gas_molecule) – E(HOF-21a + gas_molecule). Gas adsorption measurements. Gas adsorption measurements were performed volumetrically in a Micromeritics ASAP 2050 adsorption apparatus. The adsorption isotherms were obtained at temperatures from 273 K to 298 K and gas pressures from 0 to 826 mmHg. About 150 mg sample prepared by the aforementioned synthesized methodology was used for the gas adsorption studies. The initial outgassing process was carried out under a vacuum at room temperature for 12 h. The free space of the system was determined by using the helium gas. The degas procedure was repeated on the same sample between measurements for 12 h. Ultrahigh purity grade helium (99.999%), acetylene (>99%), ethylene (99.99%), carbon dioxide (99.99%), and nitrogen (99.99%) were purchased from Jingong Co., Ltd. (China). Column breakthrough experiments. In a typical experiment, 793.3 mg of HOF-21a (or 687.3 mg of MPM-1TIFSIX) ground powder was packed into a column (4.6 mm I.D. × 50 mm). The HOF-21 and MPM-1-TIFSIX sorbents were activated in Micromeritics ASAP 2050 adsorption apparatus at 298 K under high dynamic vacuum (6 μmHg), respectively. Column packing was conducted in glovebox filled with Argon. A helium flow (5 cm3/min) was introduced into the column to further purge the adsorbent. The flow of helium was then turned off while a gas mixture of C2H2/C2H4 (50:50, v/v) at 0.20 cm3/min was allowed to feed into the column.
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diffraction reveals that HOF-21 crystallizes in the orthorhombic space group Cmcm (see Table 1). As shown in Figure 1b-d, HOF-21 has a significantly different structure om MPM-1-TIFSIX (Figure 1a). HOF-21 is assembled from a discrete dinuclear paddle-wheel ionic complex [Cu2(ade)4(H2O)2]4+ in which the counter ions of SiF62- are not coordinated to the Cu2+. In the structure of MPM-1TIFSIX, the two axial positions of the Cu2+ center are occupied by the TiF62- ions, while in HOF-21 two water molecules occupy these two axial positions. These [Cu2(ade)4(H2O)2]4+ units self-assemble into a supramolecular ribbon chain, and then connected by multiple hydrogen bonding interactions between the [Cu2(ade)4(H2O)2]4+ and SiF62- segments to form a two-dimensional layer in ab plane, which further linked with SiF62- via the hydrogen bonding to generate an extrinsically porous hydrogenbonding framework (see Figures 1c and 1d). Besides, there is partial π-π stacking interaction between paralleled pyrimidine ring (see Figure 1b), which is also absent in MPM1-TIFSIX. As shown in Figure 1b, HOF-21 contains one dimensional channels of about 3.6 Å in diameter) paralleled to the c axis, which are much smaller than the pore channels of about 7.1 Å in MPM-1-TIFSIX. It is noteworthy that such alteration of ligands in axial positions in HOF-21 compared with MPM-1-TIFSIX (TiF62-) results in a significant difference in their connection style, especially the additional multiple hydrogen-bonding interactions between the [Cu2(ade)4(H2O)2]4+ and SiF62- segments, which might enhance the stability of HOF-21. The porous nature of HOF-21 revealed by crystal structure encouraged us to investigate its permanent porosity using gas adsorption experiments. Firstly, the assynthesized HOF-21 was exchanged with methanol several times, and then evacuated under dynamic vacuum at 298 K to obtain activated HOF-21 (denoted as HOF-21a), which does not uptake any N2 gas molecules at 77 K (see Figure S3). Such phenomenon has been also observed in some microporous MOFs and HOFs, and a possible explanation is that the strong interactions between N2 and the channel windows at 77 K hinder its diffusion into HOF-21.10 In this case, it might arise from the diffusion resistance because of pore size comparable to the kinetic size of nitrogen molecules. However, the CO2 gas sorption isotherm of HOF-21a at 196 K clearly indicates its microporous nature with a moderate BET surface area of 339.0 m2/g (see Figure S3).
RESULTS AND DISCUSSION
A slow diffusion of adenine solution into the mixed solution of Cu(NO3)2·3H2O and (NH4)2SiF6 at room temperature for four days yields the deep blue rectangular prismatic single crystals of HOF-21. The phase purity of HOF-21 was well confirmed by matching the experimental and simulated powder X-ray diffraction patterns (see Figure S1) and TGA (see Figure S2) and EA studies. Single crystal X-ray
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Figure 2. Experimental adsorption properties and breakthrough curves of HOF-21a and MPM-1-TIFSIX for C2H2/C2H4 separation. (a) Adsorption isotherms of C2H2 (solid) and C2H4 (hollow) on HOF-21a (blue) and MPM-1-TIFSIX (red) at 298 K. (b) Qst of C2H2 by fitting isotherms obtained at 298 K and 273 K to the Virial equation on HOF-21a (blue) and MPM-1-TIFSIX (red). (c) IAST selectivity for 50:50 C2H2/C2H4 binary mixture of HOF-21a (blue) and the other four materials including M’MOF-2a (purple), MgMOF-74 (orange), NOTT-300a (green) and MPM-1-TIFSIX (red) at 298 K. (d) Experimental column breakthrough curves for 50:50 C2H2/C2H4 binary mixture at 298 K and 1 bar in an adsorber bed packed with HOF-21a (blue) or MPM-1-TIFSIX (red). Hollow dot is for C2H4 and solid dot is for C2H2.
The establishment of permanent microporosity in HOF21a prompted us to examine its performance in gas separation especially for the industrially important C2H2/C2H4 separation and compare with MPM-1-TIFSIX. MPM-1TIFSIX (Figure 2a, red) takes up larger amount of C2H2 and C2H4 over 25 kPa than HOF-21a (Figure 2a, blue) because of its higher porosity; however, under low pressure below 25 kPa, HOF-21a takes up much more C2H2 than MPM-1TIFSIX. More importantly, HOF-21a takes up much more different amount of C2H2 and C2H4 at room temperature than MPM-1-TIFSIX, which means that HOF-21a exhibits much higher C2H2/C2H4 separation selectivity than MPM-1TIFSIX. The gas uptake of C2H2 for HOF-21a is 1.98 mmol/g at 298 K and 1 bar, while the corresponding uptake of C2H4 is 1.27 mmol/g (see Figure 2a). Apparently, HOF-21a has much higher sieving effects because of its narrower pore for the separation of C2H2/C2H4. The weakly basic nature of SiF62- also plays the roles for the preferential binding of C2H2 over C2H4.11 To understand the binding energy at low coverage, isosteric adsorption heats of C2H2 for HOF-21a are calculated using Virial equation (see Table S2). As shown in Figure 2b, the initial value of Qst for C2H2 in HOF-
21a is in the range of 36-47 kJ/mol (line blue), which are higher than those of MPM-1-TIFSIX (30-35 kJ/mol) (line red) and even comparable to those of MOFs with open metal sites,12 indicating the relatively strong interactions between the guest C2H2 molecules and host HOF-21a framework. The increase of Qst with increasing gas loading can probably be attributed to the intermolecular interaction of acetylene molecules. To further investigate the adsorption selectivity of HOF-21a and MPM-1-TIFSIX for equimolar binary mixture of C2H2/C2H4 (50:50, v/v), we performed calculations using the Ideal Adsorbed Solution Theory (IAST) with the fitted isotherms of the experimental data (Table S1). As shown in Figure 2c, at 298 K and 100 kPa, the adsorption selectivity of HOF- 21a (7.1) is comparable to that of UTSA-100a (7.4), and significantly higher than those of examined MOFs during the whole pressure range, including MMOF-74 (M=Mg, Co, Fe) (
